The intramolecular thermal cycloaddition of N-phthalimidoaziridines at multiple bonds of substituents with the intermediate formation of azomethine ylides leads to condensed pyrrole derivatives, in which the five-membered ring is adjacent to a five-, six-, or seven-membered ring. Rearrangements, which sometimes become the predominant reactions, compete with cycloaddition. Thus, aziridines with aryl substituents readily isomerize to give imines with a 1,2-shift of the phthalimide group to one of the carbon atoms. Aziridines with one electron-withdrawing substituent probably do not open to give 1,3-dipoles but rather undergo a Cope-type rearrangement involving the three-membered ring and C = O bond of the second substituent. Even in intramolecular reactions, very low activity is found for the cyano group triple bond and aromatic ring bonds as dipolarophiles.
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Notes
The yields of imines 13a and 14a were calculated using the 1H NMR spectrum of the reaction mixture relative to isolated product 12, while the yields of imines 13b and 14b were calculated from the 1H NMR spectrum of their mixture.
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This work was carried out with the financial support of St. Petersburg State University (Grant No. 12.38.16.2011).
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*Dedicated to Academician M. G. Voronkov on his 90th birthday.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1632-1648, November, 2011.
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Kuznetsov, M.A., Pan’kova, A.S., Voronin, V.V. et al. Intramolecular thermal transformations of N-phthalimidoaziridines: 1,3-dipolar cyclo-addition and rearrangements*. Chem Heterocycl Comp 47, 1353–1366 (2012). https://doi.org/10.1007/s10593-012-0921-6
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DOI: https://doi.org/10.1007/s10593-012-0921-6